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A 3:7845 0:0820x. (1)
The values of x in the Na
x
WO
3
nanostructures for the
samples annealed at different temperatures, calculated
from the above equation, have been listed in Table 1. It
should be noted that this equation is correct in the range of
0.3pxp0.85.
As can be seen from Fig. 3, (0 0 1) is the intensive peak
for the annealed samples because [0 0 1] is the major growth
orientation for Q1D nanostructures [10,23,]. Moreover,
remaining b-W (2 1 1) phase after 15 min heat treatment
shows that the lm was partially oxidized and the metal
tungsten still exists. But, this peak disappeared after 80 min
heat treatment indicating the tungsten lm was completely
oxidized under these conditions.
The optical transmission and reection spectra of the
as-deposited (0 min) and annealed lms for different
times in a range of 3001100 nm wavelength have been
shown in Fig. 4. It is seen that, the transmittance and
reectance of the as-deposited lm is lower than 8% and
around 30%, respectively. In addition, the transmittance
decreases linearly in visible range and becomes zero at
348 nm. These optical properties are in agreement with
metallic property of tungsten thin lms [24,25]. By
ARTICLE IN PRESS
Fig. 1. SEM images of sodium-doped tungsten oxide nanowhiskers after heat treatment in N
2
atmosphere at 650 1C for different times:
(a) 0 (as-deposited), (b) 15, (c) 80, (d) 80 with a higher magnication and (e) 180 min.
R. Azimirad et al. / Vacuum 82 (2008) 821826 823
increasing the heating time, the transmittance increased
while the reectance decreased. Moreover, the absorption
edge is shifted toward blue and it was determined at 320 nm
for the annealed lms. The increase of transmittance and
the occurrence of the blue-shift for the absorption edge are
associated to surface oxidation of the lms and tungsten
oxide formation. It is to note that a pure WO
3
thin lm is
highly transparent with 470% transmittance [26,27]. The
low transmittance of the annealed samples even for 180 min
ones is related to presence of sodium [21]. However, the
reduction of the reectance is attributed to rise of surface
roughness after growth of the nanowhiskers.
Finally, to understand the role of sodium in growth of
tungsten oxide nanowhiskers, a sample was prepared under
the similar growth conditions and parameters, but on a
different substrate. SiO
2
/Si(1 0 0) system (the oxidized Si
layer was prepared in O
2
ambient at 900 1C for 120 min)
was used as a substrate instead of the soda lime for growing
tungsten layer by using the same sputtering conditions.
After the annealing process for 80 min, only nanoparticles
and microparticles were observed by using SEM, without
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15 20 25 30 35 40 45 50
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
(
0
0
1
)
(
0
0
2
)
(
1
1
1
)
-
W
(
2
1
1
)
(
0
1
1
)
a)
c)
b)
x20
d)
2 (deg.)
Fig. 3. XRD spectra of tungsten thin lms after heat treatment at 650 1C
for different times: (a) 0 (as-deposited), (b) 15, (c) 80 and (d) 180 min.
0
10
20
30
40
50
60
70
80
90
0
M
o
l
a
r
c
o
n
c
e
n
t
r
a
t
i
o
n
(
%
)
O
W
Na
Si
0
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
W
(
4
f
)
W
(
4
d
)
C
(
1
s
)
W
(
4
p
3
/
2
)
O
(
1
s
)
O
(
A
u
g
e
r
)
N
a
(
1
s
)
N
a
(
A
u
g
e
r
)
S
i
(
2
p
)
S
i
(
2
s
)
0 min
15
80
180
0 min
15
80
180
40 37 34 31
Binding Energy (eV)
W
6+
W
5+
W
4+
W
0
1200 1000 800 600 400
Binding energy (eV)
200
Time (min.)
50 100 150 200
Fig. 2. (a) XPS survey spectra, (b) molar concentration of O, W, Na and Si at the surface and (c) W(4f) core level XPS spectrum of the tungsten thin lms
after heat treatment at 650 1C for different times.
Table 1
XRD peak position, lattice parameter and Na content in the Na
x
WO
3
(0 0 1) phase synthesized at 650 1C for different heating times
Annealing time (min) 2y (1) a
0
(A
) x
15 23.177 3.8350 0.61
80 23.042 3.8572 0.89
180 23.179 3.8347 0.61
R. Azimirad et al. / Vacuum 82 (2008) 821826 824
any nanowhiskers on the surface for this sample. In
addition, XPS survey spectrum of this sample determined
no sodium peaks on the surface. Therefore, it can be
concluded that diffusion of sodium from soda lime
substrate toward the surface of the lm and so its presence
on the surface plays a key role for the growth of tungsten
oxide with Q1D nanostructures. This is similar to the role
of potassium in formation of Q1D nanostructure of
tungsten oxide as reported recently [1012].
It is known that melting point of pure WO
3
is 1473 1C.
Thus, for the growth of Q1D nanostructure of WO
3
by
vaporsolid (VS) method in atmospheric pressure a high
temperature (T41000 1C) is usually needed. But, addition
of sodium as an impurity to tungsten oxide decreases the
melting point to a lower value of 698 1C for Na
2
WO
4
. We
propose a growing procedure based on the VLS mechanism
that agrees well with our experimental observations. The
VLS crystal growth mechanism was proposed by Wagner
and Ellis in 1964 for silicon whisker growth [28] and has
been widely used to guide the growth of various kinds of
one-dimensional nanostructures [29]. In our system, the
source of W is clearly the W lm, and the source of Na is
from the soda-lime substrate. It is reasonable to expect that
at the growth temperature, tiny droplets of low melting
point liquid containing Na, W and O can be produced from
the diffusion of sodium on surface of W metal and
oxidation from residual O
2
in the ambient. These tiny
droplets act as the seeds or templates for nanowhisker
growth. If more WO
3
were dissolved in the droplet to reach
the supersaturating state, solid Na
x
WO
3
would precipitate
from the droplet in the form of nanowhiskers. Continuous
feeding of WO
3
and Na into the liquid droplet sustains the
growth of the nanowhiskers. Finally, when the temperature
of the system is slowly lowered to room temperature, the
growth process was stopped. Recently, we have shown the
heat treatment of the W thin lm at 750 1C for 15 min
resulted in growth of sodium-tungsten oxide nanobelts
with U-shape cross section on the surface [30].
4. Conclusions
In conclusion, we have reported here a simple and novel
method to synthesize horizontal sodium-doped tungsten
oxide nanowhiskers on soda lime substrates at a relatively
low temperature (650 1C). This method is much simpler
than other methods reported before and can be easily
scaled up to prepare a larger amount of the material.
Annealing process for 80 min was determined as the proper
time for growing Na
x
WO
3
nanowhiskers on the surface.
Furthermore, it is determined that sodium from the soda
lime substrate diffuses toward the surface of the annealed
samples and this diffusion plays an important role in
growth and formation of the nanowhiskers.
Acknowledgments
The authors wish to thank Research Council of
Sharif University of Technology for nancial support of
the project. The assistance of Dr. M. Fathipour and
Mr. Sohrabi for SEM imaging is greatly acknowledged.
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0
5
10
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300 1100
T
r
a
n
s
m
i
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a
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(
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Wavelength (nm)
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thin lms after heat treatment at 650 1C for different times.
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R. Azimirad et al. / Vacuum 82 (2008) 821826 826